Process for purification of potable and polluted waters



Patented Aug. 11, 1936 I 2,050,398

PROCESS FOR PURIFICATION OF PO'I'ABLE AND POLLUTED WATERS Oliver M.Urbain and William R. Stemen, co-

lumbus, hio,- assignors to Charles H. Lewis, Hamster, Ohio No Drawing.Application May 10, 1935, Serial No. 20,887

6 Claims. (01. 2109) The process of the present invention relates of thesuspended and colloidal matter, are given to the purification of bothpotable and polluted as follows:- waters. By potable waters is meantwater which is being purified for domestic consumption bythe'inhabitants of a community. Waste 133. 5 In the purification ofpotable water three factors are of prime importance, namely, first.

sanitary quality, 1. e., content of bacteria, second. mm 9. p. 111.tastes and odors, and third, hardness. ifi figggg 10 The tastes andodors in potable waters are due Tannery Waste 340 10 Creamer t to thepresence in the water of organic comconcentlzlt s wagm pounds which havetheir origin in decomposing Packing muse waste organic matter or thepassage of industrial wastes into the original watershed. Bacteria,algae, The elimination of t Q 1 of th tr 5 amoeba and y other forms ofanimal and solution fraction of the various wastes is a vegetable lifeare responsible for the tastes and problem of considemme magnitude, Itis t the odors due to the dec p t o of Organic matter solution of thisproblem in the field of polluted which we find 1n ur p ta w r suppliquids and to the problem of eliminating the Many public water suppllea also contaminated tastes and odors from potable water supplies withphenols. Such is the case in many cities t the present invention is t d,

located on the Ohio River and the Great Lakes. The material employed int process consists Even a few hundredths of 1- D- D. Of P F orhydrazinated chlorinated coal. The constituwill result in a bad tasteand odor in the finished ents t actually do the work are thehydraziwater which has be chlormated- These tastes nated chlorinederivatives of coal and their derivand odors are due m large part tochlorophenols atives' Therefore the words hydrazinated 25 and chlorocchlorinated coal as used in this specification and Fo the purpose fremolfing tastes and Odors the appended claims are inclusive of thehydrapotable water supplles. actlvated carbons are now zinated chlorinederivatives of coal and their deemployed. The powdered carbon is addedto n y the water before coagulation and, after its ac- The hydrazinatedchlorinated coal is fi tlv 30 tion is complete, s coagulalied from hWater in the removal of all classes of organic compounds with aluminumsulfate and hl fie coagulants- F from water solution but is especiallyadapted to activated carbons td for 171115 Purpose are qu1e the removalof all organic acids and all compounds expensive and constitute animportant item in containing the active carhomq group. 7 the final costsof p l In the preparation of the base material we 35 The presentinvention contemplates the use of employ powdered coal such assubhitummous. a material which is not only much less expensivebituminous or anthracite coal, powdered to pass but which also willremove considerably more of through a 5 mesh to 20 mesh Screen The coalis the taste and odor producing compounds per unit i 40 of weight, andaccomplish this result in less time gehlonnated at tenolpera'ture Va groom 4 mperature to 125 C. by passing chlorine gas than the activatedcarbons now employed for the through the mass Above C the chlorine I smo e eiiic'e tfor the ur ose fro 4 ggg gif s i zonsldereg. p m compoundsdecompose, so care should be taken to In the purification of pollutedwater as keep the temperature below'this critical point. tinguished frompotable water, the requirements In this cmwmatwn processcatalysts suchas 45 are quite different. In this case, the problem inmdmel sulfur leadmay to advantage be volved is one applied to the removal of organicempmyed, though their use 15 essential- The compounds which are in truesolution, and which temperature the 031111955 rises SOmewhat (1111" areresponsible for the B. 0. D; (biochemical ins chlorination Hydrochloricacid gas and oxygen demand), of a polluted water after the Water Vaporare copiously given Smaller suspended matter and .tne colloidal matterhas quantities of 19111011 Oxides, hydrocarbons and been removed. ThisB. O. D. varies greatly for chlorinated hydmcarbons are given thedifierent wastes. The B. 0, U of a, few The product of such chlorinationcontains subu representativepolluted liquids, after the removal stantialamounts of chlorine by weight. The r from that of the original coal whenhard coals are employed. When soft coalsare employed, the chlorinatedproduct is much harder than the original coal. The chlorination shouldbe carried out in an apparatus made of materials capable of withstandingthe action of hydrochloric acid.

The action of the chlorine on the coal may be expressed by the followingfactors:

1Chlorinated substitutes for hydrogen in the hydrocarbon part of theso-called coal conglomerate.

2-Chlorine oxidizes certain groupings and opens up the ring structures.

3Chlorine adds to the unsaturated points in the coal.

4-Chlorine adds to the unsaturated points made under #2.

5Chlorine renders soluble the inactive inorganic constituents (coal ash)of the coal, such as iron and its compounds, sulfur and the alkalineearth metal compounds, which, upon removal by washing, open up the coalstructure, increasing the active surface of the mass.

6-Chlorine activates the surface of the mass by shifting the adsorbedand absorbed gases.

- By hydrazinating the chlorinated coal we have been able to materiallyincrease its activity and effectiveness-especially toward the organicacids and compounds containing the active carbonyl 'group.

The method of effecting hydrazination of the chlorinated coal will nowbe described.

The hydrazinated chlorinated coal is prepared by heating the chlorinatedcoal with any of the 'following:

1Hydrazine.

2Hydrazine hydrate.

3Salt of hydrazine.

4 Monoacyl derivative of hydrazine.

The reaction is carried out by agitating the chlorinated coal in asolution of any of the above reagents. The solution may be in water,methanol or paraflin oil. The solution should contain, not in excess of10%, of an inorganic base, such as NaOH or KOH. Catalysts, such asmetallic copper, cadmium and antimony accelerates the reaction As withthe other cases, the reaction may be eected at atmospheric pressure witha return co denser system or in a closed system at super-atmosphericpressure. The former method is more economical while the latter is morerapid.

By .the above methodsthe hydrazine molecule is substituted for part ofthe chlorine in the chlorinated coal. The general reaction is expressedas follows:

Where C-Cl=chlorine bound to whon in the chlorinated coal H I 0Cl+ N--N-G-N-N +1101 hydrazine hydrazinatcd coal The hydrochloric acid, formedby the reaction, is neutralized by the inorganic base present.

An example, showing the use of an acyl derivative of hydrazine, is givenbelow:

\ I 7C-'-Cl+ /NN CNN\ H C-CH: CCH:+HCi

acetic acid acetyl derivative hydrazide oi hydrazinated coal In thiscase it is necessary to treat the acetyl derivativeof hydrazinated coalwith hot caustic.

such as NaOH, to yield the hydrazinated coal.' The reaction of thelatter step is as follows:-

acetyl derivhydrazinated sodium ative oi coal acetate hydrazinated coalThe hydrazinated chlorinated coal is then water washed and is ready .foruse.

Hydrazinated chlorinated coal is superior to untreated coal in theremoval of all classes of organic compounds. It may be applied totheremoval of organic compounds from water solution in either of two ways:

1By the addition of the pulverized material to the water to be treated,followed by agitation and coagulation.

2By passing the water to be treated through a. filter charged with thehydrazinated chlorinated coal.

The latter of the two methods is preferred for, by this method, thematerial may be regenerated and reused repeatedly. By the first methodthe material is lost after the first using.

The organic compounds in general are removed from solution byhydrazinated coal through sorption.

The organic acids, and the compounds containing the active carbonylgroup, are removed by reaction.

The general reaction for the removal of compounds containing the activecarbonyl groups, is as follows:-

R. and R'=hydrogen or hydrocarbon radicals,

or substituted hydrocarbon radicals.

A specific example of the reaction is as follows:

'lhe'organlc acidsareremovedaceordingtothe following general reaction:

m It=hydrogen. or any hydrocarbon radical. or

a substituted hydrocarbon radical.

A specific example'showing the removal of organic acid, is as follows:

coal

The material following exhaustion may be regenerated by washing with ahot solution an inorganic acid (2% to 12%). such as H1504. or RG1;followed by washing with a solution of an inorganicbase (2% to 15%),such as NaOH or The general reactions for the regeneration (two steps),are as follows:-

'lhe inorganie'base wash also regenerates that portion oi thehydrazinated coal which may have reacted with organic acids. Thereactionisahown as toilows:---

nan n n "Mu-2V 'o +mon ----so-ri-n that-s Q used in the powdered lorm,the hydras inatedfehiorinated coal is added lust ahead ot thecoagulation step and given a 15 minuteaolagitation.Whenu'sedinpotabiewater nated the B. O. D. of the true solution tractionor organic matter present in a polluted water by treatment withhydrazlnated chlorinated coal in accordance with the described process.

Having thus described our invention, what we 10 claim is:

1. In a process for the treatment of potable and polluted waters, thestep of subjecting the water to the action oi hydrazinated chlorinatedcoal.

2. In a process for the treatment oi! potable and polluted waters, thestep of subjecting the water to the action of hydrazinated chlorinatedderivatives of coal. is

3. A process for the purification of potable waters to removeobjectionable tastes and odors comprising treating the potable waterwith bydrazinated chlorine derivatives of coal.

4. A process tor removing organic acids and all compounds including theactive carbonyl group Irom water solution comprising subjecting thewater to the action oi! hydrazlnated chlorinated coal.

' n -O-N-N=0\ +mo+msm -c-1i-1-i +o=c so n' so -n n' active use" a and \gn n n a n NaOE o-ri-n unused-m0 o Bog-H 40 coal In these examples -wehave employed sulfuric 5. A process for removing organic acids andacidand sodium hydroxide. 1 all compounds containing.the active carbonylgroup from water solution comprising the water solution through a filtercontaining hydrasinaiied chlorinated coal.

8. A process for removing organic acids and all compcimds containing theactive carbonyl chlorinatedeoal. OIIVERMURBAIN.

WILLIAMR.

